Herbicide

ABSTRACT

HERBICIDES CONTAINING A SUBSTITUTED BENZOTHIADIAZINONE DIOXIDE AND AT LEAST ONE OF A SUBSTITUTED DECAHYDROQUINAZOLINE, A SUBSTITUTED POLYCYCLIC UREA OR A BROMOAMINOPYRIDAZONE DERIVATIVE AS AN ADDITIONAL ACTIVE INGREDIENT, AND A PROCESS FOR CONTROLLING THE GROWTH OF UNWANTED PLANTS WITH THESE MIXTURES.

Patented July 30, 1974 U d t es Patent ABSTRACT OF THE DISCLOSUREHerbicides containing a substituted benzothiadiazinone dioxide and atleast one of a substituted decahydroquinazohne, a substituted polycyclicurea or a bromoaminopyridazone derivativeas an additional activeingredient, and a process for controlling the growth of unwanted plantswith these mixtures The invention relates to a herbicide containing asubstituted benzothiadiazinone dioxide and at least one other activeingredient.

It is known to use 7 plants; however,

11R denoting an isopropyl, ethyl or methyl radical or (b) a,compoundhaving theformula J on.

of the agents according to the invention.

. 1R denoting an isopropyl, isobutyl, see.-butyl or tertbutyl radical,or I (c) the compound having the formula 2 (d) compound having theformula or one of the following mixtures of the compounds: a+b+c; a+b+d;a+c+d,

have a better herbicidal, particularly selective herbicidal, action thanthe individual active ingredients.

The particular advantage of these mixtures is that they have anexcellent action on most dicotyledonous and monocotyledonous weeds andfavorable selectivity on important crop plants, e.g. rice, Indian corn,barley, wheat and rye.

The ratio of components a, b, c and d in the mixtures may be varied atwill; those mixtures of the active ingredients are preferred whichcontain a and b or c or d in the weight ratio azb or c or d of 4:1 to1:3.

The herbicides according to this invention may be used as solutions,emulsions, suspensions or dusts. The form of application dependsentirely on the purpose for which the agents are being used; in any caseit should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, the solution inwater is suitable. However, hydrocarbons having boiling points higherthan l50 C., e.g. tetrahydronaphthalene or alkylated naphthalenes, ororganic liquids having boiling points higher than 150 C. and one or morethan one functional group, e.g. the keto group, ether group, ester groupor amide group, this group or these groups being attached assubstituents to a hydrocarbon chain or being a component of aheterocyclic ring, may also be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastesor wettable powders by adding water. To prepare emulsions theingredients as such or dissolved in a solvent may be homogenized inwater or organic solvents by means of wetting or dispersing agents, e.g.polyethylene Oxide adducts. Concentrates which are suitable for dilutionwith water may be prepared from active ingredients, emulsifying ordispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active, ingredients witha solid carrier, e..g. diatomaceous earth, talc, clay or fertilizers.

The mixtures may be used as such, or in admixture with insecticides,fungicides and fertilizers.

The following experiments demonstrate the application EXAMPLE. 1 Y-witchgra'ss (Panicum capillare), green foxtail (Setaria viridis), giantfoxtail (Setaria falve'rii' (magna))', yellow foxtail (Setizria glauca),purple nutsedge (Cype ru's rotundus)", smallflower umbrella-plant(Cyperus diffo rmis),yellow nutsedge (Cyperus e sculentus), and tallumbrellaplant (Cyperus eragrostis) are treated at a hectare of each ofthe following active ingredients I3-isopropyl-2,1,3-benzothiadiazinone-(4)-.2,2;dioxide, II 1-(ar-dimethyl-fl-acetoxypropionyl)-3-isopr0pyl-2,4-dioxodecahydroquinazoline and with a mixture of active ingredients Iand II (1 kg. per hectare of 1+1 kg. per hectare of 11), these amountsof the active ingredients each being dispersed in 500 liters of waterper hectare. After a few days it is observed that the mixture of activeingredients I+II has, in comparison to the individual active ingredientsI and II, a superior herbicidal action and more favorable selectivity oncrop plants.

The results of the experiment are given in the following table:

Active ingredient Mixture I II I+II Application rate kg-Iheetare 1 2 1 21+1 Cropplants:

On za sativa 0 0-10 0-10 30 0 0 0 0 20 0 Ipomoea sp 50-60 80 70 100 100Polygmmm persica1ia 90 100 70 90 100 Fee amma 0 90 90-100 90-100 .Poairivzalis 0 10 90 90-100 90-100 -Cynodondactylon 10 20 80 90-100 1Echinuchloa crus-gjrlli. 10 20-30 80 90-100 90-100 Digitariasanguinalis0-10 1 70 90 80 Panicum'cqpillare. 0-10 10 80 90-100 80-90 Seturiaviridis 10 20-30 80 1 90-100 Setariafaberti (magna).-.- 0-10 10 70-80 80Setaria glguca 0 0-10 80 90-100 80-90 C'ypema rotundus 70-80 90-100 0100 Cyperus dz'fl'omzia" 90 100 0 0-20 100 C'uperus esculentus. 50 80 2040 80 Cyperus esagrostisnn 80 90-100 40 70 100 NOTl].-0 No damage. 100Total destruction.

These results show that the herbicides according to the invention have asurprising action on broadleaved and grassy weeds and, in particularexhibit selectivity which could not be inferred from the action of thecomponents of the mixture.

EXAMPLE 2 A field with rice (Oryza sativa), Indian corn (Zea mays),ladysthumb *(Polygonum persicaria), chickweed (Stellaria media), meadowgrass (Poa trivialis), barnyard grass (Echinochloa crus-galli), foxtailspecies (Setaria sp.) and purple nutsedge (Cyperus rot'andas) growing onit is treated per hectare with the mixture of '1 kg. of3-isopropyl-2,1,3-benzothiadiazinone-(4) 2,2-dioxide and 11 kg. of1-(a,u-dimethyl-fl-acetoxypropionyl)3-isopropyly-2,4-dioxodecahydroquinazoline dispersed in 500 liters ofwater per hectare. After 14 days it is ascertained that all broadleavedand grassy weeds are almost completely withered; no damage to rice andIndian corn is observed.

EXAMPLE 3 The plants barley (Hordeum vulgare'), wheat =(Triticum:vulgare), rye '(Secale cereale), camomile -(Matricaria chamom illa),false comomile (Matricaria marigrowth" heiglitof hem-3'- to20emrwith-I"anfl"2"kg;per""' "hectare ofIIDf-the'se ainonntsbf theactive ingredients ing table:

Active ingredients Mixture I III I+I1I Application rate kg.lhectare.,- 23 1 3 2+1 Cro lants: I

ordeum vulgare 0 0-10 '0-10 30-40 0-10 Tjriticum vulgare- 0 30 0 Seealecereale 0 0-1 0 0-10 30 0-10 Unwanted plants:

Matricaria chamomilla 100 1 00 90 1'00 100 M alricaria maritime- 90 10090 100 100 Anthemis arvensis. 100 100 90 100 100 Sinapis arvensis 9090-100 90-100 100- .100 Polygonum persz'caria 100 100 40 60-70 100Chrysanthemum segetumm 100 100 70 100 100 Lamium amplezicaule 80 100 7090 100 Galium (marina... 70 ,90 10-20 30-40 90 Lolium perenne 0-10 1090-100 100 100 Alopecurus myosuro 10 10-20 100 100 100 PM annua 10 10-20100 100 100 Apera spice venti 10 10-20 100 100 100 NOTE.-0=N0 damage.100=Total destruction. I

These results show that the herbicides according to the invention have asurprising action onbroadleaved and grassy weeds and, in particular,exhibit selectivity which could not be inferred'from the action of thecomponents of the mixture.

, EXAMPLE 4 in 500 liters of water per. hectare. After 14 days it istima), corn comomile (Anthemis arvens'is), ladysthumb (P0lyg0numpersz'caria), corn 'marigold (Chrysanthemum 'segetum), henbit (Lam iumamplexicaule'), Catchweed bedstraw :(Galium aparine) perennial rye.grass (Lolium perenne),-slender .-foxtail (Alopecums myasuraides),annual bluegrass (Poa annua) and-silky .bent grass (Apera spica venti)are treated in agreenhouse at a-growth height of '6 to 20 cm. with--arnounts-,correspending to-2 and B- kg. hectare of -3-isopropyl-2,1,3-benzothiadiazinone-M)-2,2-di0xide. 1(1), with amounts corresponding toland 3 kg. per hectare of N-[l-yor-Z- (3a,4,-5,6,7,7a hexahyd ro .4,7methanoindanyl).]-N'- N-dimethy-lurea (1H), and. with a mixtureof activein.- gredients [I and III '(2 kg. per hectare of 1+1 kg. per

ascertained that the broadleaved tnd grassy weeds 'are almost completelywithered, whereas the crop plants barley, wheat and rye continue to growwithout damage.

EXAMPLE 5 In a greenhouse, the plants barley (Hordeum vulgare), wheat(Triticum vulgare), rye (Secale cereale), camomlle (Matricariachamomilla), corn camomile (Anthemis arvensis), corn marigold(Chrysanthemum segetum), henbit (Lamium amplexicaule), catchweedbedstraw (Galium aparine), .annual bluegrass (Poa annua), slenderfoxtail (Alopecurus myosuroides) and silky bent grass (Apera spicaventi) are treated at a growth height of 4 to 18 cm. with amountscorresponding to 1.5 and 3 The results of the experiment 6 EXAMPLE 7 Ina greenhouse, the plants large crabgrass (Digitaria sanguinalis),barnyard grass (Echinochloa crus-galli), green foxtail (Setariaviridis), yellow nutsedge (Cyperus esculentus), bermudagrass (Cynodondactylon) and redroot pigweed (Amaranlhus rety-oflexiis) "are treated ata Actwemgmdwnt Mlxture growth height of 3 to 20 cm. with 1.5 kg. perhectare of I V 3-isopropyl 2,1,3 benzothiadiazinone-(4)-2,2-dioxideApplication ratekgJhectare-.. 1.5 a 1.5 3 1.5+1.5 Wlth P hectare of -i0F Cm Ian hexahydro-4,7-methanomdanyl)] N,N' dimethylurea ii iardemhvulgare 0 0-10 0-10 30 040 (III), with 0.75 kg. per hectare of1-phenyl-4-amino-5- Triiicum vulgare 0 0 0 -30 0 e weak-m 0 M0 (H0 2H0(H0 laromopyridazone (6) (IV), and with a mixture consist Unwantedplants: mg of 1.5 kg. per hectare of I+-0.75 kg. per hectare ofMatrz'caria chumtmilla..- 100 100 80 100 100 Matricaria maritime 00 10070 90-100 90-100 r d '7 kgiper hectare i an of fliese amqunts ofAnthe'misarvensis 100 100 80-90 90100 100 10 active ingredients eachbeing dispersed in 500 liters of CM aanthemum magnum" 100 100 90 100 100Lani/mm amplmwuzemn 70% 100 so 100 90400 water per hectare. After 4Weeks, the act on of the active Gall-um apart-L 1038 90 133 138 38ingredients and the mlxture on the plants 1s ascertained by Poa annuaAlopewms u deg (H0 1H0 8H0 mo 90 determining thelr fresh weight (meanfigures taken as rela Apera spice venti 0-10 10-20 100 100 100 tivevalues compared with untreated plants (=100)). It

20 is ascertained that the mixture of lH-III-t-IV has in com- N '11:. =Nd m e. 100=Totaldestrueti0n.

ag parlson to the indivldual active ingredients reduced the welght ofthe plants to a very considerable extent.

The results of the experiment are given in the following table:

Fresh weight (relative) Digitarta Echino- Amaranthua Appllcntlonsanguinchloa erus- Seiaria Cypems Oynodon retro- .Active lngredlent ratealts galli airidis esculentus dactylon flezus Untreated 100 100 100 100100 100 I 1. 5 89.5 88.9 35 19. s 100 99. s m 0. 75 20 5. 4 25. 5 s0 so0.75 25.2 14.9 00 61.3 24.9 I+III+IV 1.s+0.75.0.75 3.7 1.0 2.3 9.4 0.45.8

EXAMPLE 6 On an a ricultural site the lants barle (Hordeum g P y EXAMPLE8 vulgare), wheat (Triticum vulgare), rye (Secale cerea-le), annual bluegrass (Poa annua), ladysthumb (Polygonum persicaria), catchweedbedstra-w (Galium aparine), slender foxtail (Alopecurus myosuroides) andwild oats (Avena fatua) are treated at a growth height of 3 to 20 cm.with 1.5 kg. per hectare of3-is0pr0ply-2,1,3-benzothiadiazinone-(4)-2,2-dioxide (I), with 0.75 kg.per hectare of N-[lor2(3a,4,5,6,7,7a-hexahydro-4,7-methanoindanyl)]-N',N'-dimethylurea (III),with 0.75 kg. per hectare of 1-phenyl-4-amino 5 bromopyridazone-(6)(IV), and with a mixture consisting of 1.5 kg. per hectare of I+0.75 kg.hectare of III'+0.7S kg. per hectare of IV,

all these amounts of the active ingredients each being dispersed in 500liters of water per hectare. After 4 weeks, the action of the activeingredients and the mixture on the crop plants and broadleaved andgrassy weeds is ascertained by determining their fresh weight (meanfigures taken as relative values compared with untreated plants (:100).It is ascertained that the fresh weight of cereals from the treatedplots, and particularly in the case of the mixture of I+III+IV, is insome instances somewhat higher than in the case of the untreated plots,and the weight of the broadleaved and grassy weeds, in contrast to theuntreated plots, decreases to such a great extent that only a few gramscan be ascertained.

The results of the experiment are given in the following table:

On an agricultural site the plants Indian corn (Zea mays), annualbluegrass (Poa arnnua), barnyard grass (Echinochloa crusgalli), purplenutsedge (Cyperus rotundus) and ladysthumb (Polygonum persicaria) aretreated at a growth height of 3 to 20 cm. with 2 kg. per hectare of3-isopropyl 2,3 benzothiadiazinone-(4)-2,2-dioxide (I), with 0.5 kg. perhectare of 1-(u,a-dimethyl-fl-acetoxypropionyl)-3-isopropyl 2,4dioxodecahydroquinazoline (II), with 0.5 kg. per hectare of N-[l or2-(3a,4,5,6,7,7ahexahydro 4,7 methanoindanyl) ]-N,N'-dimethylurea (III),and with a mixture consisting of 2.0 kg. per hectare of I+0.5 kg. perhectare of II+0.5 kg. per hectare of III, all these amounts of theactive ingredient each being dispersed in 500 liters of water perhectare. After 4 weeks, the action of the active ingredients.- and themixture on the plants is ascertained by determining their fresh weight(mean figures taken as relative values compared with untreated plants(=l00) The fresh weight of Indian corn on the treated plot correspondsapproximately to that on the untreated plot, but the weight of thebroadleaved and grassy weeds on the treated plot is reduced to such agreat extent that only a few grams can be ascertained.

The results of the experiment are given in the following table:

Fresh weight (relative) Folygonum Alopecurus Active Hordeum TriticumSecal Poa pers i- Galinm myqsu- Arena ingredient Application ratevulgare vulgare cereals annua caria aparme routes lama 100 100 100 100100 100 100 100 IUftreated 1. s 101. 2 105 100 75. 4 5. 4 40 80. 5 III.0. 75 98. 5 96. 5 25 59 89. 4 20 25 IV- 0. 75 100 107. 5 100 30. 5 14. 760 36. 5 B9. 5 I-l-III-l-IV 1.5+0.75+0.75 101. 0 100 102. 2 12. 1 2. 624. 4 14. 7 10 On an agricultural site the plants Indian corn (Zeamays), catchweed bedstraw (Galium aparine), false camomile (Matricariamaritima) and slender foxtail (Alopecurus myosuroiaes) are treated at agrowth height of 3 to 20 cm. with 2 kg. per hectare of3-isopropyl-2,3-benzothiadiazinone-(4)-2,2-dioxide (I), with 0.5 kg. perhectare of l-(a,a-dimethyl B acetoxypropion'yl)-3-isopropyl-2,4-dioxodecahydroquinazoline (II), with 0.5 kg. per hectare of1-phenyl-4-amino 5 bromopyridazone-(6) (IV), and with a mixtureconsisting of 2 kg. per hectare of I+0.5 kg. per hectare of II+0.5 kg.per hectare of IV, these amounts of the active ingredients each beingdispersed in 500 liters of water per hectare. After 4 weeks, the actionof the active ingredients and the mixture on the plants is ascertainedby determining their fresh weight (mean figures taken as relative valuescompared with untreated plants (=100)). In comparison with the untreatedplot, the mixture of I +II+IV and the individual components slightlyincrease the fresh weight of Indian corn; in comparison with theindividual components and the untreated plot, the mixture of I-l-II-l-IV reduces the fresh weight of Galium aparine, Matricaria maritimaand Alopecurus myosuroides to a considerable extent.

The results of the experiment are given in the following table:

1. A herbicide containing a herbicidally efiective amount of a mixtureconsisting essentially of (a) a compound having the formula thesalts Rdenoting an isopropyl, ethyl or methyl radical or a salt thereof, and(b) 1-phenyl-4-amino-5-bromopyridazone-(6) in a respective Weight ratioof compounds a and b of 4:1 to 1:3. 4. A process as claimed in claim 3wherein compound (3) is3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-diox- 1 e.

References Cited UNITED STATES PATENTS 3,210,353 10/1965 Reichender etal. 7l 92 FOREIGN PATENTS 25,594 1968 Japan 71 91 LEWIS GOTTS, PrimaryExaminer C. L. MILLS, Assistant Examiner U.S. Cl. X.R. 71-92, 119

UNITED STATES PATENT AND TRADEMARK FFIQE CERTIFICATE @F nowwn PATENT NO.26,642

DATED July 30, 1974 INVENTOMS) 3 Adolf Fischer It is certified thaterror appears in the above-identified patent and that said LettersParent are hereby corrected as shown below:

First page, insert --[30] Foreign Application Priority Date March 19,1969 Germany a a a a P l9 l3 850u2-- Column 8, line 15, "1:1" shouldread --l:3-

Signed and sealed this 15th day of July 11.975.a

(SEAL) Attest:

C, MARSHALL DANN Commissioner of Patents and Trademarks RUTH C. MASONAttesting Officer

